508 SCREENING OF SELECTED FLUOROAROMATIC COMPOUNDS FOR USE AS AGRICHEMICALS, I R. H. Shiley, D. R. Dickerson, Claus Grunwald, and J. R. Willard • A W\ /\ j% mr WjlWj/ M^tms. \\ ^^m^wK\X^I^i (WsJ^\f^J i*ffiw'^ f ^ Lrv^ Jm Pj $jW) Illinois Institute of Natural Resources ILLINOIS STATE GEOLOGICAL SURVEY DIVISION, URBANA, ILLINOIS Jack A. Simon, Chief CIRCULAR 508 1979 Shiley, Richard H Screening of selected fluoroaromatic compounds for use as agrichemicals, I / by R. H. Shiley and others. ■- Urbana : Illinois State Geological Survey Division, 1979. 17p. : tables ; 28cm. (Illinois-Geological Survey. Circular ; 508) References: P. 1 1 . 1 . Fluoroaromatic compounds. 2. Herbicides- Testing. 3. Fungicides-Testing. I. Title. (Series) SCREENING OF SELECTED FLUOROAROMATIC COMPOUNDS FOR USE AS AGRICHEMICALS, I R. H. Shiley, D. R. Dickerson, Claus Grunwald, and J. R. Willard ILLINOIS STATE GEOLOGICAL SURVEY Urbana, Illinois 61801 Jack A. Simon, Chief Circular 508, 1979 CONTENTS Abstract 1 Introduction 1 Experimental procedures 1 Fungicides 1 Foliar disease protectant 2 Curative 2 Systemic 2 Soil fungicide 2 Herbicides 2 Preemergence 2 Postemergence 3 Arabidopsis thaliana (L.) Heynh Assay 3 Tomato pedicel test 3 Ethylene evolution test 3 Results and discussion 3 References 1 1 Appendix A. Compound index. 12 Appendix B. Other compounds tested for biological activity. 14 TABLES 1 . Organisms causing disease. 2 2. Fungicide evaluation. 4 3. Pre- and postemergence herbicide evaluation. 6 4. Effects on the growth of Arabidopsis thaliana. 9 5. Tomato pedicel explant test. 10 6. Ethylene evolution test. 11 ACKNOWLEDGEMENTS The authors wish to thank the Agricultural Chemical Division of FMC Corporation, Middleport, NY, for their help in the screening program and especially Dr. Arthur A. Ramsey for his help in com- piling this data. We also acknowledge the assistance of Dr. Glenn Finger, Alberta Zachay, and Gail Gray and express our gratitude for their efforts. SCREENING OF SELECTED FLUOROAROMATIC COMPOUNDS FOR USE AS AGRICHEMICALS, I R. H. Shiley and D. R. Dickerson, Illinois State Geological Survey, Urbana, IL Claus Grunwald, Illinois State Natural History Survey, Urbana, IL J. R. Willard*, Agricultural Chemical Division, FMC Corporation, Middleport, NY ABSTRACT A series of 214 fluoroaromatic compounds were screened for biological activity for use as fungicides and herbicides. Fungicidal activity was tested in the following four categories: foliar, curative, systemic, and soil. In the foliar fungicide evaluation, three of the subject compounds showed slight to moderate activity against leaf spot of sugarbeet and bean rust. As curative agents, six of the compounds showed good activity when compared to Ben- late in controlling leaf spot of sugarbeet, bean powdery mildew, and cucumber powdery mildew. Systemically, one compound showed only slight control of tomato bacterial spot. In the soil fungicide evaluation, six of the test com- pounds showed moderate to good activity against fusarium root rot of bean and cucumber damping-off when com- pared to Benlate. Of the eleven compounds which exhibited pre- or postemergence herbicidal activity, 2,4,5-trifluoro- phenoxyacetic acid was the most effective. It is comparable in activity to its chloro analog. Twenty-five field crops and weeds were used in the herbicide evaluation. The testing of the gross effects on the growth of Arabidopsis thaliana and the ethylene evolution test were also used in the screening program. INTRODUCTION Forty years of research in organic fluorine chemistry in the laboratories of the Illinois State Geological Survey has made available for research purposes a large number of aromatic fluorine compounds. The Illinois State Geological Survey traditionally has had an interest in plant growth regulators (Finger et al., 1959). As early as 1951, the Botany and Plant Pathology Section of the Illinois State Natural History Survey was testing fluorinated p-benzo- quinones for their fungicidal activities (Tehon, 1951). In 1954, Forsberg tested 1-fluoro-3-methyl-4,6-dinitrobenzene and 1,3-difluoro-4,6-dinitrobenzene for protection against Fusarium rot in Gladiolus corms. These compounds were very effective. ♦deceased In 1974, fifty-one fluoroaromatic compounds were tested on several fungi which attack Gladiolus corms, and Poinsettia plants and cause dutch elm disease (Shiley et al., 1975). Seven of the compounds tested had a fungicidal activity equal to or greater than that of mercuric chloride on one or more of the organisms tested. As a result of these findings and the Geological Survey's recent publication Aromatic Fluorine Chemistry at the Illinois State Geological Survey, Research Notes 1934- 1976 (Shiley et al., 1978), coupled with recent advances with the potassium fluoride-halogen exchange reaction on polychloro-benzenes (Forsberg, 1954; Shiley, Dickerson and Finger, 1972/73; Shiley, Dickerson, and Finger, 1978; Shiley et al., 1975; Tehon, 1951) which allows for increased ease of synthesis of these compounds, the desire to test the subject compounds as agrichemicals has been rekindled. Therefore, a new program designed to test 214 aromatic fluorine compounds under industrial and field conditions was undertaken in a cooperative study between the Agri- cultural Chemical Division of the FMC Corporation (Middleport, NY) and the Illinois State Geological Survey Geochemical Section and under the guidance of the Illinois State Natural History Survey, Botany and Plant Pathology Department. This work will be expanded in the future to include the testing of some of these compounds as insecti- cides and nematicides. EXPERIMENTAL PROCEDURES The synthetic routes and physical constants for the compounds used in this screening program are reported in Illinois State Geological Survey Circular 501 (Shiley et al., 1978). The methods employed in this screening program are the basic testing procedures used by the FMC Corpora- tion Agricultural Chemical Division. The various testing procedures are as follows. Fungicides The organisms employed in this biological screening program are described in table 1 . SCREENING OF SELECTED FLUOROAROMATIC COMPOUNDS The biological tests used in the screening program are as follows: 1. Foliar disease protectant. Test results are reported as the percentage of control of infection due to treatment of the host plant with test chemical one day prior to inoculation with the fungal organism. 2. Curative. Test results are reported as the percent- age of control of infection due to treatment of the host plant with test chemical one day after inocu- lation with the fungal organism. 3. Systemic. Test results are reported as the percent- age of control of infection of the host plant due to treatment of the soil with the test chemical one day prior to inoculation of the plant with the disease organism. 4. Soil fungicide. a. Fusarium root rot. Test results are reported as the percentage of control of infection of the plant due to treatment of the soil with test chemical one day prior to inoculation of the soil with fungal organism. b. Cucumber damping-off. Test results are re- ported as an efficacy index (El) which com- pares the effect of the test chemical to that of a standard (Captan). El greater than 100 indicates that the test chemical is more effective than the standard. Calculation of the efficacy index is shown below. In this test, cucumber seeds are treated with the test chemical, planted in soil, and subsequently inoculated with the disease complex. Tot. stand,. . . , -Tot. stand, . ,, (test chem.) (untreated) Herbicides The plant species employed in the preliminary bio- logical screening program are as follows: Common name Lima bean Sweet corn Wild oats Lettuce Mustard Crabgrass Scientific name Phaseolus lunatus L. Zea mays L. Avena fatua L. Lactuca sativa L. Brassica juncea (L.) Czerniak Digitaria sanguinalis (L.) Scop. El = Tot. stand, „ . _ , .-Tot. stand, . (Captan stand.) (untreated) x100 The following biological tests are used in the screening program: 5. Preemergence. In the preemergence test, the test chemical is sprayed onto the seeds at planting. Test results are recorded after 10 to 14 days. Test results are reported as a qualitative measure of the vigor (V) of standing plants/percentage of plants killed (K). Vigor ratings are assigned as follows: Vigor ratings 1 - Severe injury. Plants are not expected to recover. 2 - Moderate to severe injury. Severe injury to surviving plants. 3 - Moderate injury. Plants are expected to recover. 4 - Slight injury. Plants have recovered or are expected to fully recover. 5 - No effect. TABLE 1. Organisms causing diseases. Disease Fungus Host plant Cultivar Late blight Bean rust Rice blast Leaf spot Bean powdery mildew Bacterial spot Root rot Damping-off Phytophthora infestans (Mont.) d By. Uromyces phaseoli (Pers.) Wint. Pyricularia oryzae Cav. Cercospora beticola Sacc. Erysiphe polygoni DC. Xanthomonas vesicatoria (Doidge) Dows. Fusarium solani (Mart.) Appel and Wr. f. phaseoli (Burk.) Synyd. and Hans. Pythium ultimum Trow Rhizoctonia solani Keuhn tomato (Lycopersicon esculentum L.) Heinz 1350 bean [Phaseolus vulgaris L.) Pinto rice (Oryza sativa L.) Nova 66 sugarbeet (Beta vulgaris L.) A436-67R bean (Phaseolus vulgaris L.) Bountiful tomato (Lycopersicon esculentum L.) Heinz 1350 bean (Phaseolus vulgaris L.) Pinto cucumber (Cucumis sativus L.) Straight Eight ILLINOIS STATE GEOLOGICAL SURVEY/CIRCULAR 508 The plants are also examined for any biological growth responses. These are denoted by the letter R. The growth effects screened for are as follows: Biological response (R) 1 - Necrosis 2 - Stunting 3 - Desiccation 4 - Axillary growth stimulation 5 - Nastic responses 6 - Necrotic spots 7 - Growth stimulation 8 - Defoliation 9 - Chlorosis 10 - Intumescence For example a 20/3/2 rating indicates that 20 percent of the plants were killed by the test chemical treatment, there was moderate injury to surviving plants, and the surviving plants were stunted in growth. 6. Postemergence. Test results are reported as in the preemergence test. In the postemergence test, 10 to 14 day old plants are sprayed with the test chemical. Test results are recorded after an addi- tional 10 to 14 days. The same standards for vigor ratings (V) and the biological growth responses (R) are used as those for the preemergence tests. 7. Arabidopsis thaliana (L.) Heynh Assay. Arab- idopsis seed is placed in a culture tube containing a solidified mixture of test chemical and agar- nutrient culture medium. The culture tubes are placed in a growth chamber and grown under controlled environmental conditions for the duration of the plant life cycle (approximately 35 days). The regulatory effects noted are: seed germination, root elongation, root geotropism, number of rosette leaves, fresh weight, abnormal leaf morphology, time to bolting, internode length, days to flowering, abnormal flower morph- ology, and fruit weight. The application rates were 0.01, 0.1, 1.0, 10, and 100 ppm. 8. Tomato pedicel test. The pedicel with abscission layer is excised from the flower and set on a filter paper in a petri dish. A solution of the test chem- ical in acetone is applied to the filter paper. The test is then conducted in a controlled environment chamber, and the inhibition or acceleration of abscission is noted. The number of abscised pedicels is recorded 1, 2, 4, 5, and 7 days follow- ing the treatment. The application rates were 0.1, 1.0, 10, 100, and 1000 ppm. Each treatment rate was replicated twice with 10 pedicels. Water was used as a control. 9. Ethylene evolution test. The primary leaf abscis- sion zones including the petiolar base abscission layers are excised from 2 to 3 week old lima bean plants. One ml_ of test solution is added to a vial containing the test tissue and 0.1 mM of indole acetic acid. The vials are stoppered and placed in a controlled environment chamber. Ethylene evolution is analyzed by gas liquid chromato- graphy 24 hours following treatment. The regula- tory effects noted are the induction of ethylene evolution in plant tissue, or the release of ethylene by degradation of the applied chemical. The data is reported as ethylene/mg of tissue. The rates of application were 0.01, 0.1, 1.0, 10, and 100 ppm. Cycloheximide and Ethephon were used as controls. RESULTS AND DISCUSSION The fungicide testing program (table 2) involved four different methods of treatment: foliar, curative, systemic, and soil fungicide. In the foliar fungicide evaluation, 2,6-difluoro-3,5- dinitrochlorobenzene (1)* and 2-fluorobenzoic acid hy- drazide (2) showed only slight activity in the control of leaf spot of sugarbeet. 2,2'-Difluoro-5,5'-dihydroxydi- phenyl sulfide (3), however, demonstrated moderate activity against bean rust as compared to Daconil 75 WP. When 2,6-difluoro-3,5-dinitrochlorobenzene (1) and 2- fluorobenzoic acid hydrazide (2)' were tested as curative agents against leaf spot of sugarbeet, and against bean and cucumber powdery mildew, moderate to good activity was demonstrated as compared to the test standard Benlate. 2,2'-Difluoro-5,5'-dihydroxydiphenyl sulfide demonstrated good activity at the 450 ppm level against bean powdery mildew, but the activity fell off rapidly at the lower rates. None of the tested compounds demonstrated any systemic activity on tomato bacterial spot except for 2- trifluoromethyl-4-fluoroaniline (4), and this was only slight. Activity comparable to Benlate was demonstrated by methyl 2-fluoro-6-hydroxybenzoate (7), and 2,4-dinitro- 5-methylfluorobenzene (8) in the control of root rot of bean. Three other compounds including 2-trifluoromethyl- 4-fluoroaniline (4) were effective at higher rates of application. 'Refers to compound number listed in Appendix A. SCREENING OF SELECTED F LUOROAROMATIC COMPOUNDS TABLE 2. Fungicide evaluation. Compound number Biological test and chemical used 16.7 Percentage of disease control at indicated rate (ppm) 50 150 450 Foliar protectant 1 2 Leaf spot of sugar beet 2,6-Difluoro-3,5-dinitrochlorobenzene 2-Fluorobenzoic acid hydrazide Benlate 50 WPb Bean rust 2,2'Difluoro-5,5'-dihydroxydiphenyl sulfide Daconil 75 WPb 0 4 13 0 8 3 98 100 100 0 35 71 80 100 100 Curative 1 2 d Systemic Leaf spot of sugar beet 2,6-Difluoro-3,5-dinitrochlorobenzene 2-Fluorobenzojc acid hydrazide Benlate 50 WPb Bean powdery mildew 2,6-Difluoro-3,5-dinitrochlorobenzene 2-Fluorobenzoic acid hydrazide 2,2'-Difluoro-5.5'-dihyroxydiphenyl sulfide Benlate 50 WP Cucumber powdery mildew 2,6-Difluoro-3j5-dinitrochlorobenzene Benlate 50 WP Tomato bacterial spot 2-Trifluoromethyl-4-fluoroaniline 21 48 85 98 10 71 87 94 48 92 94 98 76 78 85 97 71 87 87 93 - 0 35 95 95 100 100 100 . 0 8 100 95 100 100 100 Rate (mg/pot) 0.4 1.3 3.8 11.3 Soil fungicide Fusariurn root rot of bean N(2-Fluorophenyl)glycine hydrazide 4-Fluoro-3-nitrobenzoic acid Methyl 2-fluoro-6-hydroxybenzoate 2-Trifluoromethyl-4-fluoroaniline 2,4-Dinitro-5-rnethylfluorobenzene Benlate 50 WPb 19 4 15 Cucumber damping off 2-Nitro-3-trif luoromethylphenol Captan - 0 89 - 0 56 50 71 71 0 40 92 36 50 61 38 63 70 Efficacy index at indicated rate (mg/pot) 1.3 3.8 0 100 63 100 11.3 77 100 Testing procedure number 1 Standard 'Testing procedure number 2 ^Testing procedure number 3 'Testing procedure number 4a Testing procedure number 4b ILLINOIS STATE GEOLOGICAL SURVEY/CIRCULAR 508 When compared to Captan, 2-nitro-3-trifluoromethyl- phenol (9) showed moderate activity against cucumber damping-off. Three other fungicidal screening tests were used in this study: the foliar and systemic tomato late blight and the curative rice blast. Little or no fungicidal activity was found in any of these three areas. In general, the compounds evaluated in the fungicide screening program did not exhibit enough control to warrant continued testing. The pre- and postemergence herbicide testing results can be found in table 3. The test compounds were sub- jected to a preliminary screening at the rate of 8.96 kilo- grams/hectare. Six plant species (lima bean, corn, wild oats, lettuce, mustard, and crabgrass) were used in the screening. If the compounds showed some activity, purple nutsedge was added to the list and they were tested at decreasing application rates from 8.96 to 0.56 kilograms/ hectare. In some cases, as many as twenty-five field crops and weeds were used. 2,4,5-Trifluorophenoxyacetic acid (18) was extensively studied at decreasing rates from 8.96 to 0.07 kilograms/hectare in both the pre- and postemer- gence evaluation. 2,4,5-Trifluorophenoxyacetic acid (18) showed good activity when compared to 2,4,5,-trichloro- phenoxyacetic acid, especially in the preemergence test. However, most of the compounds screened in the pre- and postemergence herbicide test showed little or no effect at or below the 2.24 kilogram/hectare application rate. A number of the compounds which exhibited some activity in the pre- and postemergence herbicide testing were further investigated for biological activity by studying their gross effects on the growth of Arabidopsis thaliana (table 4) and subsequently for activity in the tomato explant test (table 5) and the ethylene evolution test (table 6). Arabidopsis thaliana is an excellent test plant for biological testing because of its short life cycle. In a rela- tively short period of time (approximately 35 days), the gross biological effects starting with seed germination and ending with seed production can be monitored. In this study, 2,4,5-trifluorophenoxyacetic acid (18) exhibited the greatest effect on the growth of the Arabidopsis thaliana plant. This compound was toxic at application rates as low as 1 ppm and had measurable effects on the fresh weight and the fruit weight at 0.01 ppm. In general, the other compounds tested were toxic at 10 to 100 ppm and showed little effect except on the fresh weight and the fruit weight at doses just below toxic levels. 2-Trifluoromethyl-3,4-dichloro-6-fluoroaniline (22), how- ever, showed an increase in the fresh weight of the Arab- idopsis thaliana specimen. At rates less than toxic on all compounds tested for growth effects, root elongation, leaf morphology, and flower morphology were all normal. Root geotropism was positive in all of these cases. Therefore, these factors were omitted from table 4. Because of its high activity, 2,4,5-trifluorophenoxy- acetic acid (18) was also evaluated in the tomato pedicel explant test (table 5). In this case the number of abscis- sions is dramatically inhibited at application rates as low as 0.1 ppm. 2-Fluoro-6-bromobenzoic acid (23) also showed some inhibition at the 1 ppm dose level. Isopropyl N(3,4-difluorophenyl)carbamate (12), ethyl N(4-fluorophenyl)carbamate (21), and isopropyl N(4- fluorophenyl)carbamate (13) exhibited inhibition only at higher doses near the toxic level. This activity decreased to near the control values at lower doses. The water control values started with one abscission on the first day and rose rapidly to 15 after 7 days. 2-Trifluoromethyl-3,4-dichloro-6-fluoroaniline (22) showed little if any effect on abscission rates. All of the compounds tested in the tomato pedicel explant test were toxic at the 1000 ppm application rate. This application rate was eliminated from table 5. Five of the subject compounds were evaluated in the ethylene evolution test (table 6). This test is important in the screening of compounds for stimulating ripening of fruits and vegetables. It is difficult to get clear-cut answers from the results of this test. Although the method used in the ethylene evolution test is sound and controls are maintained on variables such as the ages of plants used, the values for cycloheximide and ethephon (controls) vary strikingly with different experiments. Therefore, each group of test plants within the ethylene evolution series must be viewed individually and the results must be considered in a general overview with the other activity evaluations done on each of the compounds. A better judgement of the gross biological effects of each compound tested can then be made. In addition to the 23 compounds listed in tables 2 to 6, 191 other compounds were tested for biological activity, but because of their poor or complete inactivity these have been omitted from tables 2 to 6 and instead are listed in Appendix B by their chemical names. SCREENING OF SELECTED FLUOROAROMATIC COMPOUNDS , . rsi (N CM , , CN CN CN ■ m . (V r>J M (N . CM Ol . , CN CN CN (N CN CN CN CN in in v co ^ in in in in co v in in o co co in m m , co co cm in ^ m co ^ v ro in m co ro in v ^ co CO CO co ^ co v o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o m . m v in n v n 9 t in o o o o o o o o o o o o o o o CN , CN , CN cn .in *■ . *■ . co — ~ K -Q a S 3 2 5 J5oi 2 | u J il -l Sod! o _| 9 E .-i u in CO 2 s am O £ ? £ -o o. .£ o S o _i o g 2 K 13 a E _ E2 ILLINOIS STATE GEOLOGICAL SURVEY/CIRCULAR 508 CM , w- , (Ni- m » c c > i;£.. .3:"p«; c E Jo5J5 .o a 65 SCREENING OF SELECTED F LUOROAROMATIC COMPOUNDS 5 E _3 z£ E 5 3C — — *- . O inn , w n co n i n i ■ CM . t- CM «- . CM CM . , CM ' TjcM^rn.CMcoro.CMCM. , cm ^t O O CM , Oi . If) . *- *- *- fM rsi CM , IT) (N . rotj- . if> in . cm o cm , m (N . n'j^mrM^ijcNnn^nin . •- ^r ^ ro *j o n . cm n Olfi>- , fjr- , If) (N . in CM .If) n *r *r . (tj in c i- cm ro tj if) CO ,- CM CO tT Lf) C ILLINOIS STATE GEOLOGICAL SURVEY/CIRCULAR 508 TABLE 4. Effects on the growth of Arabidopsis thaliana Average values for 4 replications treatment rate (ppm) Compound Chemical number name Response Control 0.01 0.1 1 10 100 10 2-Chloro-6-iodofluorobenzene Seed germination, days 3 5 3 3 4 > Fresh weight (mg) 121 103 96 115 104 Number of rosette leaves 11 10 11 10 10 T Rosette bolting, days 16 16 16 16 16 T Internode length (mm) 20 30 38 26 33 T Flowering, days 21 21 21 21 21 T Fruit weight (mg) 20 .9C 18 14 19 26 T 12 Isopropyl N (3,4-d if luoro phenyl (carbamate Seed germination, days 3 3 3 3 3 3 Fresh weight (mg) 110 113 111 99 T T Number of rosette leaves 11 10 10 10 T T Rosette bolting, days 17 17 17 17 T T Internode length (mm) 30 31 25 29 T T Flowering days 24 21 21 23 T T Fruit weight (mg) 13.6 14.4 14.6 15.1 T T 13 Isopropyl N(4-fluoropheny I (carbamate Seed germination, days 3 3 3 3 3 5 Fresh weight (mg) 110 99 118 95 67 T Number of rosette leaves 11 9 10 9 9 T Rosette bolting, days 17 17 17 17 17 T Internode length (mm) 30 32 32 22 24 T Flowering, days 24 21 22 22 24 T Fruit weight (mg) 13.6 16.8 15.2 17.3 3.5 T 18 2,4 ,5-Tr if luorophenoxy acetic acid Seed germination, days 3 3 3 3 3 5 Fresh weight (mg) 121 80 60 T T T Number of rosette leaves 11 9 10 T T T Rosette bolting, days 16 16 16 T T T Internode length (mm) 20 34 18 T T T Flowering, days 21 21 21 T T T Fruit weight (mg) 20.9 8.8 3.7 T T T 21 Ethyl N(4-fluorophenyl)carbamate Seed germination, days 4 4 4 4 4 T Fresh weight (mg) 111 129 125 69 T T Number of rosette leaves 10 9 9 10 T T Rosette bolting, days 19 19 19 19 T T Internode length (mm) 26 39 35 24 T T Flowering, days 24 22 24 25 T T Fruit weight (mg) 23.4 25.6 19.5 5.3 T T 22 2-Trifluoromethyl-3,4-dichloro-6-fluoroaniline Seed germination, days 4 4 4 4 4 4 Fresh weight (mg) 111 156 142 111 147 T Number of rosette leaves 9 10 10 10 10 T Rosette bolting, days 19 19 19 19 19 T Internode length (mm) 26 33 38 19 28 T Flowering, days 24 23 22 23 25 T Fruit weight (mg) 23.4 23 22.7 27 10 T 23 2-Fluoro-6-bromobenzoic acid Seed germination, days 4 4 4 4 T T Fresh weight (mg) 111 125 125 126 T T Number of rosette leaves 10 9 10 10 T T Rosette bolting, days 19 19 19 19 T T Internode length (mm) 26 24 31 25 T T Flowering, days 25 25 25 25 T T Fruit weight (mg) 23.4 26.4 22.4 9.7 T T Testing procedure number 7 mT = Toxic 'Value for a single surviving replicate SCREENING OF SELECTED F LUOROAROMATIC COMPOUNDS TABLE 5. Tomato pedicel explant test Compound number Chemical name Day 0.1 Number abscissed out of 20 rate (ppm) 10 100 12 Isopropyl N(3,4-difluorophenyl)carbamate 3 11 12 12 12 12 13 Isopropyl N(4-f luoropheny I (carbamate 8 9 13 13 13 3 7 9 10 10 18 2,4,5-Trifluorophenoxyacetic acid 21 Ethyl N(4-fluorophenyl)carbamate 2 12 16 16 16 3 11 11 11 11 22 2-Trifluoromethyl-3,4-dichloro-6-fluoroaniline 5 9 11 11 12 7 13 14 14 14 5 10 11 11 11 23 2-Fluoro-6-bromobenzoic acid 1 8 8 10 10 Testing procedure number 8. Water control values were 1 on the first day and rose rapidly to 1 5 after 7 days. "T = Toxic. 10 ILLINOIS STATE GEOLOGICAL SURVEY/CIRCULAR 508 TABLE 6. Ethylene evolution test Compound number Chemical name 0.01 Ethylene/mg tissue rate (ppm) 0.1 10 100 10 18 20 22 23 2-Chloro-6-iodofluorobenzene 2,4, 5-Trifluorophenoxy acetic acid Cycloheximide Q Ethephon Untreated check Ethyl N(3-chloro-4-fluorophenyl)carbamate Cycloheximide Ethephon Untreated check 2-Trifluoromethyl-3,4-dichloro-6-fluoroaniline 2-Fluoro-6-bromobenzoic acid Cycloheximide Ethephon Untreated check 8 7 13 9 8 27 16 16 32 151 60 5,663 112 112 13 28 7 15 13 57 24 36 18 71 79 214 90 72 15 5 8 28 17 47 10 33 50 107 83 244 373 145 17 3 11 50 4 2 284 2788 13 16 117 4 6 2 192 216 61 18 118 68 89 58 74 9 2,034 25,005 111 58 Testing procedure number 9. Average of two replicates. 'Standard. j Average of 5 replicates. REFERENCES DICKERSON, D. R., G. C. FINGER, and R. H. SHILEY, 1972, Reaction products of pentachlorobenzene with potassium fluoride in dimethyl sulfoxide: Transactions of the Illinois State Academy of Science, v. 65, nos. 3 and 4, p. 75-80. (Illinois State Geological Survey reprint 1974-F, 6 p.) Journal of Fluorine Chemistry, v. 4, p. 111-113. (Illinois State Geological Survey reprint 1974-K, 3 p.) FORSBERG, J. L., 1954, A summary of 1953 gladiolus disease control tests in Illinois: Illinois State Florists Bulletin, p. 153. DICKERSON, D. R., G. C. FINGER, and R. H. SHILEY, 1973/ 1974, Polyphenyl fluorides: Journal of Fluorine Chemistry, v. 3, p. 113-116. (Illinois State Geological Survey reprint 1973-1, 4 p.) FINGER, G. C, D. R. DICKERSON, and R. H. SHILEY, 1971/ 1972. Fluorination of 1,2,3,4 and 1,2,3,5 tetrahalobenzenes with potassium fluoride in dimethyl sulfone: Journal of Fluorine Chemistry, v. 1 , p. 415-425. (Illinois State Geological Survey reprint 1972-M, 1 1 p.) SHILEY, R. H., D. R. DICKERSON, and G. C. FINGER, 1972/ 1973, Fluorination of 1 ,2,3-,1 ,2,4-, and 1 ,3,5-trihalobenzenes with potassium fluoride in dimethyl sulfone: Journal of Fluorine Chemistry, v. 2, p. 19-26. (Illinois State Geological Survey reprint 1972-T, 8 p.) SHILEY, R. H., D. R. DICKERSON and G. C. FINGER, 1978, Aromatic fluorine chemistry at the Illinois State Geological Survey, Research notes, 1934-1976: Illinois State Geological Survey Circular 501 , 1 14 p. FINGER, G. C, M. J. GORTATOWSKI, R. H. SHILEY, and R. H. WHITE, 1959, Aromatic fluorine compounds. VIII. Plant growth regulators and intermediates: Journal of the American Chemical Society, v. 81, p. 94-101. (Illinois State Geological Survey reprint 1959-G, 8 p.) SHILEY, R. H. J. L. FORSBERG, R. S. PERRY, D. R. DICKERSON, and G. C. FINGER, 1975, Fungicidal activity of some fluoroaromatic compounds: Journal of Fluorine Chemistry, v. 5, p. 371-376. (Illinois State Geological Survey reprint 1975-A, 6 p.) FINGER, G. C, R. H. SHILEY, and D. R. DICKERSON, 1974, A synthesis of 1 ,2,3,4-tetrafluorobenzene by KF fluorination: TEHON, L. R., 1951, Fungistatic potencies of fluorinated p-benzo- quinones: Science, v. 1 14, p. 663. SCREENING OF SELECTED FLUOROAROMATIC COMPOUNDS 11 Appendix A— Compound Index Number Name Empirical Molecular formula weight Structure 1 2,6-Difluoro-3,5-dinitrochlorobenzene C6HCIF2N204 238.53 2 2-Fluorobenzoic acid hydrazide C7H7FN20 154.14 11 12 2,2'-Difluoro-5,5'-dihydroxydiphenyl sulfide C12H8F202S 254.25 4 2-Trifluoromethyl-4-fluoroaniline C7H5F4N 179.12 5 N(2-Fluorophenyl)glycine hydrazide C8H10FN3O 183.19 6 4-Fluoro-3-nitrobenzoic acid C7H4FN04 185.11 7 Methyl 2-fluoro-6-hydroxybenzoate C8H7F03 170.14 8 2,4-Dinitro-5-methylfluorobenzene C7H5FN204 200.12 9 2-Nitro-3-trifluoromethylphenol C7H4F3N03 207.11 10 2-Chloro-6-iodofluorobenzene C6H3CIFI 256.44 Isopropyl N(2,5-difluorophenyl) carbamate Isopropyl N(3,4-difluorophenyl) carbamate CioHnFjIMOj 215.20 C10H,,F2NO2 215.20 (continued) O, N F <§>c' 02N F U^)>CONHNH2 o>-s-<5> HO OH F \0/nhcH: N02 F (C)S COOH CONHNH- >COOCH3 OH N02 F CH3 F3 C N02 0,N CN 15 Ethyl N(3-trifluoromethylphenyl) carbamate C10H,0F3NO2 233.19 FSC NHCOOCH2CH3 16 Isopropyl N(3-trifluoromethylphenyl) C,iH,2F3N02 247.22 carbamate CH3 NHCOOCH \ CH3 17 2-Nitro-4-fluorophenoxyacetic acid C8H6FN05 215.14 NO, f/Q\och2cooh 18 2,4,5-Trifluorophenoxyaceticacid C8H5F303 206.12 F(IJ >OCH2COOH F 19 2-Fluoro-4-nitrophenol C6H4FN03 157.10 02NOH 20 Ethyl N(3-chloro-4-fluorophenyl) carbamate C9H9CIFN02 217.63 Cl F<( ))NHCOOCH2CH3 21 Ethyl N(4-fluorophenyl)carbamate C9H,0FNO2 183.18 F<( )>NHCOOCH2CH3 22 2-Tr if luoromethy 1-3,4 ,-dichloro-6- fluoroaniline C7H3CI2F4N 248.01 Cl CF3 Cl/0/NH2 F 23 2-Fluoro-6-bromobenzoic acid C7H4BrF02 219.01 r